Production of foamed articles

ABSTRACT

POLYURETHANE FOAM ARTICLE COMPRISING A FOAM FORM INTERIOR PORTION AND A THICK, SUBSTANTIALLY NON-FOAM FORM, CROSS-LINKED SKIN SURFACE PORTION INTEGRA WITH SAID FOAM FORM INNER PORTION, WHICH ARTICLE WAS MADE BY FOAMING POLYURETHANE MATERIALS IN A MOLD HAVING INTERNAL SURFACES COATED WITH AN ORGANO-TIN POLYURETHANE CROSS-LINKING AGENT.

y 27, 1971 HANS-DIETRIICH mus 5 5 PRODUCTION OF FOAMED ARTICLES Filed March 1.3, 1969 INVENTOR HANSDIETRICH KRUG kW 2 y ATTORNEYS.

United States 3,595,734 PRODUCTION OF FUAMED ARTICLES Hans-Dietrich lKrug, Heidelberg, Germany, assignor to Carl Freudenherg K.G., Weinheim/Bergstrasse, Germany ()riginal application July 18, 1966, Ser. No. 566,009, now Patent No. 3,468,991, dated Sept. 23, 1969. Divided and this application Mar. 13, 1969, Ser. No. 840,560 lint. Cl. 1832b /14, 5/20; B29d 27/00 US. Cl. 161-160 2 Claims ABSTRACT OF THE DHSCLUSURE Polyurethane foam article comprising a foam form interior portion and a thick, substantially non-foam form, cross-linked skin surface portion integral with said foam form inner portion, which article was made by foaming polyurethane materials in a mold having internal surfaces coated with an organo-tin polyurethane cross-linking agent.

This application is a division of application Ser. No. 566,009, filed July 18, 1966, now US. Pat. No. 3,468,991.

This invention relates to foamed articles. It more particularly refers to a process for the production of polyurethane foam articles having a protective coating thereon.

The manufacture of polyurethane materials is quite well known. These materials are the reaction and polymerization products of isocyanatoor isothiocyanato-contaim'ng compounds and compounds containing active hydrogen such as acids, alcohols, amides, etc. It is well known to utilize both aromatic and aliphatic diisocyanates and diisothiocyanates, such as for example tolylene diisocyanate or hexamethylene diisothiocyanates, in the production of these polymers. Suitable, known active hydrogen-containing compounds used to make polyurethanes are polyesters and polyethers, as exemplified by polyethylene adipate and polypropylene oxide, which polyester may be either carboxylor hydroxylterminated, as desired.

It is known to produce foamed articles comprising polyurethane by providing the polymerization reaction mixture with a blowing agent of some sort. It has been found to be quite desirable in many cases to provide foamed polyurethane articles with a protective layer which is relatively non-foam in structure.

Production of this type of article has in the past been accomplished in a two step process. The foam article of desired shape and size has been produced and a suitable protective skin of appropriate size and shape has been produced. These two parts have then been joined by gluing or other suitable means to form the desired final article. It has also been proposed to produce a protective layer or skin in the form of a pouch and then to produce the polyurethane foam inside the pouch whereby the desired composite article is produced.

As can be seen, prior art methods have generally required two articles to be separately produced and then joined together to form the desired end product. It will be appreciated that this type of production is in need of improvement since it would be desirable to carry out the production of the desired articles discussed above by a less cumbersome process.

It is therefore an object of this invention to provide a novel process for the production of articles of polyurethane foam having a protective layer thereon.

It is another object of this invention to provide an article structurally consisting essentially of a polyurethane having a foamed interior and a substantially non-foam exterior.

It is a further object of this invention to provide a novel apparatus in which an article as described above can be produced.

Other and additional objects of this invention will become apparent from a consideration of this entire specification including the claims appended hereto.

In accord with and fulfilling these objects, this invention includes as one of its aspects a shaped article structurally consisting essentially of a polyurethane and having an integral foamed interior and substantially non-foam exterior.

According to this invention, this article is produced by introducing a polyurethane foam-forming composition into a mold, which mold has interior walls which are substantially non-adherent with respect to the foam-forming composition as well as with respect to the final product; subjecting the contents of the mold to foam-forming conditions; and removing the desired product from the mold. It has been discovered, most surprisingly, that, when the mold walls are of a non-adherent material, the produced article has a substantially non-foam protective layer around the outside and is substantially foam on the inside. It has been found to be particularly useful to provide as the inside walls of the mold a silicone rubber, a halogenated polyolefin or an organo-tin compound. It is necessary in the practice of this invention that the nonadherent inside surface of the mold be continuous since it has been found that, where there are discontinuities in this surface, the protective layer is irregularly and incompletely formed, particularly because, in removing the finished article from the mold, some of the protective layer tends to remain attached to these discontinuities. Thus, the finished article does not have a complete protective layer.

It is preferred in the practice of this invention that the mold be charged with polyurethane foam producing material in such proportion that the total volume of foam which would be produced under atmospheric pressure conditions would be greater than the volume of the mold cavity. It is desirable that the foaming process produces an internal pressure in the mold such that the foam produced is forced against the mold walls. The most preferred internal pressure generated by the foaming of at least several atmospheres, suitably up to about atmospheres or more may be provided, but care should be taken that the pressure generated is not so great that the foamed article is caused to adhere to the mold walls.

It is within the spirit and scope of this invention to utilize molds forming polyurethane foams which have walls composed entirely of the above-referred to non-- adherent composition. It may be practical to reinforce these walls to retain the internal pressure built up on the mold as in conventional practice. It is also within the scope of this invention to provide conventionally constructed metal (or other suitable material) molds of the desired size and shape and then to provide a suitable non-adherent coating on the inside walls of the mold.

The non-adherent inside mold Walls have been stated to preferably consist of silicone rubber, fluorinated polyolefins or organo-tin compounds. Exemplary of the organo tin compounds are tin ethylhexylate, tin isooctate, tin ricinoleate, tin naphthenate, di-n-bu'tyl tin dilaurate. These tin compounds are suitably applied dissolving them in a suitable solvent, benzene for example, applying the solution to the inside wall of the mold and then evaporating the solvent. Such tin salt may be applied directly to metal mold surfaces. It is preferred, however, to provide an intermediate layer between the organo-tin compound and the metal mold wall. For example, silicone resins and polyester resins have been found to be suitable for use in this application.

It is within the spirit and scope of this invention to provide metal mold walls with a silicone rubber coating as suggested above, to use this material for preparing foam polyurethane articles according to this inventiOn and then, after making several of such foam articles, to coat the silicone rubber with a suitable organo-tin compound, whereupon additional articles can be produced efficiently according to this invention. It has been found to improve efficiency if the organo-tin compound is periodically applied to the inside walls of the mold at some reasonable interval, for example, after every 50 to 100 moldings.

Silicone rubbers have been mentioned as suitable mold wall coatings. These are exemplified by Giesmasse 56 sold by A. Wacker, Munich, or mixtures thereof.

- Fluorinated polyolefins have been mentioned as suitable mold wall coatings. These are exemplified by tetrafiuoroethylene and polychlorotrifiuoroethylene.

Suitable surface coatings according to this invention may be applied in layers up to any desired thickness. It has been found that coatings up to about 2 mils are generally satisfactory.

It is most desirable that, when using a silicone rubber or an organo-tin internal mold wall or coating, thereon, the polyurethane forming materials be substantially anhydrous. This is important since significant quantities of water may have a deleterious effect upon the mold walls, sometimes causing them to hydrolyze, or being responsible for local overheating and turbulent foam formation. By substantially anhydrous is meant that the water content is about weight percent or below, preferably about 1.5 percent or below.

The polyurethane foam forming materials used in this invention are those generally used commercially or are otherwise conventionally known. The polymerization and foaming techniques are all conventional with the proviso that the internal pressure generation described above is provided.

The foaming is suitably carried out at about 100 C. over a period of about 5 to minutes. After foaming is complete, it is preferred to permit the foam article to cool in the mold, and after such cooling to about to 70 C. to remove such from the mold.

The following example is given by way of illustration of this invention without being limiting thereon.

EXAMPLES A foam-forming composition of about parts of poly ethylene adipate and about 40 parts of tolylene diisocyanate containing about 5 parts of a conventional piperazine derivative catalyst and as a blowing agent about 1% water is used as a charge. A mold as illustrated in FIGS. 1 and 2 is used. As there shown the mold comprises an outer support member as for instance the ring member of steel or the like 1 carrying an inner insert 2 of U-shaped cross section and providing the upper ring 3. The mold is substantially flexible and because of its flexibility readily removable from the support 1. The mold is preferably made of a nonadhering material or at least carries a contact surface -(for the foam) of such material. In this example the mold itself was made of a cold-vulcanized silicone rubber and specifically one made by use of di-n-butyl-tin-laurate as a catalyst.

The cold-vulcanizable silicone product is for instance conventionally composed of dimethylpolysiloxane with conventional fillers and catalysts and suitable conventional filling and softening agents. Such material is for instance available on the market in Germany as Giesmasse 56 by Wacker-Chemie G.m.b.H. in Munich, Germany.

The above described charge starts to react soon after the components are mixed together and is therefore filled into the insert 2 as quick as possible after co-mixing. The plates 4 and 5 are clamped together and the foam formation proceeds with a temperature rise.

The reaction proceeds rapidly. After cooling the plates 4 and 5 are removed and the mold insert 2 is easily removed from the support 1. The molded object is then easily removed from the flexible insert and the object upon examination is foamed to have a substantially nonfoam protective layer on all surfaces of contact with the mold.

This protective layer is smooth, relatively compact and corresponds in every detail to the surface walls of the mold including any design ornamentation which the same may contain as for instance leather stitching or the like.

The surface layer is an integral part of the foam object and is produced by the surface action between the foamed material and the highly active cross-linking means produced by the tin component with the mold.

The same mold may be used several times. Since the cross-linking agent such as the two components above mentioned is thereby continuously removed from the surface of the mold material, the latter will develop a relatively hard surface no longer as efiiciently usable for molding purpose is it was when new. It is therefore necessary to coat the surface of the mold insert with any suit able conventional highly active cross-linking agent for the foam material to be foam-molded in the mold insert. Within this specification suitable active cross-linking materials are a tin-ethylhexylate, tin-isooctate, tin ricinoleate, tin naphthenate, di-n-butyl-tin-di-laurate. The latter gives particularly advantageous results. These tin compounds are applied by way of their easily sprayable solutions in benzene, the solution being sprayed at the inside of the mold insert and permitting the solvent to evaporate.

In alternative examples there were additionally added small amounts of parafiin, silicone oil and other conventional adhesion preventing agents. Best results are obtained by using about equal amounts of the adhesion preventing material, the cross-linking agent and the solvent except that in those cases where more viscose components and particularly of .the cross-linking agent are used it is desirable to improve the sprayability of the wetting component by adding further amounts of solvents. Best results were obtained by the use of a conventional silicone oil as the same is for instance marketed as Silikonol AK AOE.OOO by Wacker-Chemie GmbH in Munich. When using silicone oil as an additive the integral compacted surface layer on the foam material has a particularly pleasing and smooth appearance similar to that of polished leather.

It is in most cases desirable to obtain the integral crosslinked layer of non-foamed material in a thickness of an order of magnitude of at least 0.05 and preferably 0.2 of a millimeter and the products obtained in accord with the herein discussed examples have these integral layers the extent of at least about 0.2 mm.

What is claimed is:

1. A moldable article of polyurethane consisting essentially of a single aliquot of cross-linkable, foam forming polyurethane in a closed mold in contact with non-adherent interior mold surfaces coated with an organo tin catalyst for cross-linking said polyurethane, whereby upon foaming of said polyurethane in said mold an integral non-foamed surface layer of cross-linked polyurethane covering at least part of a foamed core portion is obtained.

2. An article as claimed in claim 1 wherein said nonfoam surface layer is about 0.005 to 0.2 mm. thick.

References Cited UNITED STATES PATENTS 3,468,991 9/ 1969 Hans-Dietrich Krug 26445 FOREIGN PATENTS 664,192 6/1963 Canada 264-45 W. J. VAN BALEN, Primary Examiner Us. 01. X.R.

WW5? UNITED STATES PATENT OFFICE b9 CERTIFICATE OF CORRECTION Patent No. 3595734 Dated July 27 1971 Inventor(s) Hans-Dietrich Krug It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 4, line 3, after "is" "foamed" should read --found-- Column A, line 41, "AOE.OOO" should read O0.000-- Column 4, line 50, after "'layers" insert --to-- Signed and sealed this 25th day of January 1972.

SEAL '11 At'test:

ammo M. FLETCHER, JR. ROBERT GOTTSCHALK lime-sting Officer Commissioner of Patents 

